Petroleum & Coal

ISSN 1337-7027

Available online at www.vurup.sk/pc

Petroleum & Coal 52 (3) 164-172, 2010

THERMAL CRACKING OF THE MODEL SEVEN COMPONENTS

MIXED PLASTICS INTO OILS/WAXES
Martin Bajus, Elena Hjekov
Slovak University of Technology, Faculty of Chemical and Food Technology,
Institute of Organic Chemistry, Catalysis and Petrochemistry, Radlinskho 9,
SK-812 37 Bratislava, Slovakia, e-mail : martin.bajus@ stuba.sk
Received May 3, 2010, Accepted August 2, 2010

Abstract
In a previous paper we have reported thermal cracking of individual and mixed plastics into
oil/waxes. Now we are getting insight into thermal cracking of model seven components mixed
plastics. Thermal cracking of mixture composed of high-density polyethylene (HDPE) /low-density
polyethylene (LDPE) /linear-low-density polyethylene (LLDPE) /polypropylene (PP)/polyvinyl
chloride (PVC)/ polyethyleneterephthalate (PET) /polystyrene PS/ (HDPE/LDPE/LLPE/PP/PS/PET/
PVC = 34.6/17.3/17.3/9.6./9.6./10.6/1.1 %wt.) was carried out in the batch reactor at
temperatures from 350 to 500oC in atmospheric pressure. The main objective of this study was
converting the seven components mixed plastics into oil/wax product for use as hydrocarbon fuel
oil or chemical feedstock. The effect of temeperature and reaction time have been studied to
ascertain the optimum conditions necessary for the production as well as to investigate the effects
of these parameters on the composition of pyrolysis products, with special emphasis on the
oil/waxes.
Keywords: Thermal cracking; pyrolysis; mixed plastics; oil/waxes; characterization.

1. Introduction
Pyrolysis is one of the best methods for preserving valuable petroleum resources in
addition to protecting the environment by decreasing the volume of non-degradable waste.
Pyrolysis of waste plastics is favored because of the high rates of conversion into oil, which can
be used as fuel or feedstock in refinery. The gaseous products coming from the pyrolysis
process with high caloric value may also be used as fuel. Recycling by pyrolysis has high
potential for heterogeneous waste plastic materials, as the separation is not economical.
There has been a plethora of research work on the pyrolysis of individual and mixed plastics.
Plastic polymers make up a high proportion of waste and this is expected to continue
in the future with the dramatic increase in the volume and range of plastic products in use.
The two main types of plastic are: thermoplastics which soften when heated and harden
again when cooled and thermosets which harden by curing and cannot be re-moulded.
Thermoplastics are by far the most common types of plastics comprising almost 80% of
the plastics used in Western Europe. There are six main component plastics in European
municipal solid waste which are high-density polyethylene (HDPE), low density polyethylene
(LDPE), polypropylene (PP), polystyrene (PS), polyvinylchloride (PVC) and polyethyleneterephthalate (PET). However, the polyethylene plastics, LDPE and HDPE make up over
40% of the total plastic content of municipal solid waste. The consumption of plastics in
Western Europe is of the order of 38 million tones per year [1] and it is estimated that only
50% of the plastics produced are available for collection and recycling.
The low grade uses for mixed plastic recycled materials has led to research into alternative
processing methods to produce higher value products. One example is via chemical recycling
where the plastic waste materials are processed back to produce basic petrochemicals, that
can be used as feedstock to make virgin plastic [2, 3]. Feedstock recycling can be via hydrogenation at high temperature and pressure to thermally degrade the plastics. Pyrolysis of
waste plastics is a recycling option that shows great potential and has been investigated by a
number of researchers [4-9]. Pyrolysis is the thermal degradation of the plastics in an inert

M. Bajus, E. Hjekov/Petroleum & Coal 52(3) 164-172, 2010

165

atmosphere and produces gas, oil and solid char products. The yield and composition of
the products is influenced by a range process parameters, including the type of waste
plastic and reactor system, but also other factors, such as the gas residence time, temperature
and pressure ranges, presence of catalyst, and presence of hydrogen gas or hydrogen
donor compounds [10-14].
In our previous reports, we have also reported on the copyrolysis of individual low-density
polyethylene and polypropylene with naphtha [8], copyrolysis of two component mixture
(LDPE/PP) [9, 15] and three component mixture (LDPE/HDPE/PP) [9, 15] with naphtha. The
composition of gaseous and liquid products during copyrolysis was studied at 780oC and
820oC. The utilization of oils/waxes obtained from thermal cracking of individual LDPE,
HDPE, LLDPE, PP or cracking mixed polymers PP/LDPE, HDPE/LDPE/PP and HDPE/LDPE/
LLDPE/PP for the production of automotive gasolines and diesel fuels was overviewed [11].
Polystyrene degraded at around 350oC, mainly into viscous dark-colored oil. The
formation of char was dramatically enhanced at 450 and 500oC, reaching up to 30%
wt.. The oil product from PS even at 350oC consisted almost entirely of aromatic
compounds especially toluene, ethylbenzene and styrene [12, 14]. In the work Almazn
Almazan et al. [6] carbonization time and carbonization temperature were a major
factors in the composition of products during PET pyrolysis. Pyrolysis of mixed plastics
containing PVC produces inorganic and organic chlorine compounds during the initial
stages of pyrolysis process [5, 19]. The presence of PET in municipal waste plastic
(MWP) produced the additional chlorinated hydrocarbons.
In the present investigation, we report the thermal degradation of the model seven
components mixed waste plastics carried out in the batch reactor at 450oC in atmospheric
pressure. The effect of PS, PET and PVC in model mixed plastics on the quality of liquid
products was presented. The detailed investigation on the distribution PS, PET and PVC in
various degradation products is discussed. GC was used for the analysis of liquid products
obtained from PE/PP/PS/PVC/PS/PET thermal degradation.
In this study, HDPE/LDPE/LLDPE/PP/PS/PVC/PET represents common plastics
usually present in high proportion in the plastic waste stream of municipal solid
waste. The main objective of this study was to convert the waste plastics into oil/wax
product for use as a hydrocarbon fuel oil or raw chemical feedstock. The effects of
temperature and reaction time have been studied to ascertain the optimum conditions
necessary for the production of oil/wax as well as to investigate the effects of these
parameters on the compositions of reaction products, with a special emphasis on the
oil/waxes. Reaction (residence) time here refers to the length of time (run in minutes)
for which an experiment was held at a particular (constant) temperature. The choice
of this term is intended to avoid the confusion of using the term, reaction time,
residence time and run time which would inadvertently include both the reactor heatup time and actual reaction time or residence time.
2. Experimental
2.1. Materials
The feedstocks used in our presented work were obtained from the Slovak Republic.
The characteristic for all feedstocks have been evaluated for the temperature 25oC.
2.1.1. Polymers
Main characteristic of used polymers is in table 1. Polymers were virgin plastics in the
form of pellets, except of PET (bottle) and PVC (powder).
Table 1 Characteristic of used polymers
Polymer
HDPE
LDPE
LLDPE
PP
PS
PVC
PET

Mw

Mn

, kg.m-3

33 800
292 000
112 110
200 000
173 000
62 500

6 950
22 000
30 300
65 000
135 135
86 500
25 000

950
919
919
903
1 050
1 380
920

producer
Slovnaft, a.s.
Slovnaft, a.s.
Slovnaft, a.s.
Slovnaft, a.s.
Plastika, a.s.
Plastika, a.s.
waste

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166

2.2. Thermal cracking of polymer blend

We used a similar apparatus as in our previous works [8, 11], with cooler traps operating at
70 C. 10 %wt. solution of sodium hydroxide was used for gas produced from seven-component
mixture for catching of chlorine, which is present in the PVC. The presence of halogen
compounds in the oils/waxes prevents the oils/waxes to be used as fuel or refinery feedstock.
The presence of chlorine in the oil/wax cannot exceed 10 ppm [5, 19]. The batch reactor
was fed with 17 g of feedstock and closed. Nitrogen as inert gas (50 ml.min-1) was fed
into the apparatus to prevent the presence of oxygen in the reactor. Thermal cracking
took 92 min. at 450oC and 116 min at 500oC. The following program for thermal cracking
of polymer blend was used: heating rate of 16.5oC.min-1 to 350oC, 8 min temperature
stabilization, heating rate of 9 oC.min-1 up to 440oC, heating rate of 7.5 oC.min-1 up to
480oC. However, final real temperature in the reactor was 450oC. The temperature was
controlled by thermocouples. The convenient rate heating and duration of polymers cracking
for the production of high yields of oil/waxes was determined to be 92 min. and 116 min.
as result of the optimization procedure. Detailed description of thermal cracking is given
in literature [8, 11]. Obtained products were: yellow oils/waxes collected in the separator,
gas collected in the gas sample, brown residue in the reactor.
The composition of seven-components polymer blend used as feedstock is shown in
Table 2. In many countries, plastic is collected from commercial and industrial sources as
separate plastic fractions, much of which is recycled directly back into the plastic product
manufacturing process. Although plastic make up between 5 and 15 mass % of municipal
solid waste it comprises 20 30% of the volume [1]. There are five main plastics which
arise in Slovakia municipal solid waste. PE (65 mass %), PP (9%), PS (9%), PET (10%),
PVC (1%), rest (PA, ABS, PMMA, and others) (6%) [16].
o

Table 2 The composition of polymer blend

Plastic sample

weight [g]

mass %

HDPE

5.87

34.57

LDPE

2.94

LLDPE
PP

Plastic sample

weight [g]

mass %

PS

1.63

9.57

17.29

PET

1.81

10.64

2.94

17.29

PVC

0.18

1.07

1.63

9.57

Total

17.00

100.00

2.3. Analysis of gaseous and liquid products from thermal cracking

Analysis of the gases obtained from thermal cracking of polymer blend was performed
with the gas chromatograph Hewlet Packard HP 6890+. The three-PLOT chromatographic
column system consists of two parallelly installed detectors FID and TCD and of three switching
valves. Helium was used as a carrier gas. The temperature in the injection chamber was
150oC. The time of analysis was about 40 min.
The liquids obtained from thermal cracking were analyzed with the gas chromatograph
CHROM 5. The gas chromatograph system consists of the DB-PETRO column and the FID
detector. Helium was used as a carrier gas. The temperature in the injection chamber
was 240oC. The time of analysis was about 80 min. The analytical procedure was described in
detail in [8, 9].
2.4. Results and discussion
The thermal cracking of HDPE/LDPE/LLDPE/PP/PS/PVC/PET blend was performed
under atmospheric pressure at 450oC and 500oC. The products of plastic cracking were
classified into three groups: gas, liquid (oil/wax) and solid residue. Table 2 shows the
yields of thermal cracking products. Thermal cracking of HDPE/LDPE/LLDPE/PP/PS/PVC/
PET blend resulted in 30.5 35.5 % wt. of gas, 62.3- 65.9 % wt. of oil/waxes and 2.13.6 % wt. of brown solid residues. The oil/waxes (62.3- 65.9 % wt.) produced with the
seven components polymer blend were lower than yield of oil/wax for individual polyethylenes
(~ 79 80 % wt.), PP (85 % wt.) and mixed polymers 79 82 mass %) [10, 11]. It is clear
from the Table 3 and Table 4 that the presence of PS, PVC and PET has predominant
effect on the formation and yields of gases and oil/waxes in the comparison with the
thermal cracking of individual and mixed polymers (Table 4).

M. Bajus, E. Hjekov/Petroleum & Coal 52(3) 164-172, 2010

167

Table 3 Products yield of thermal cracking at 450C and 500C

Temperature, oC

450
Yield
Gas

Oil/w
ax
11.20

%wt.

65.94

500
Yield
Solid residue

Oil/wax

Gas

Solid residue

5.18

0.61

10.60

6.04

0.36

30.47

3.59

62.35

35.53

2.12

Table 4 Product composition obtained during thermal cracking of polymers at 450C

Feedstock
LDPE
HDPE
LLDPE
PP
LDPE/PP
LDPE/HDPE/PP
LDPE/HDPE/LLDPE/PP
LDPE/HDPE/LLDPE/PP/PVC/PS/PET
a)

a)

Oil/wax
79.8
79.8
79.1
85.0
79.4
82.4
79.7
75.4

Yield, Y/ %wt.
Gas
15.1
17.0
12.6
14.2
17.2
13.8
14.4
21.9

LDPE/HDPE/LLDPE/PP/PVC/PS/PET in % wt. 16.0/32.0/16.0/32.0/0.8/2.5/0.8/

[10,11]

Residue
5.1
3.2
8.3
0.9
3.4
3.8
5.9
2.7

This results has not been found only in the actual monitored representation of PS (9.6 % wt.),
PVC (1.1 %wt.) and PET (1.6 %wt.), but it has been found also in a considerably lesser
representation of PS (2.5 %wt.), PVC (2.7 %wt.) and PET (0.8 %wt.) in a previously
pyrolysed mixture with published results [10]. The most difficult problems arose during
pyrolysis of the actual PET. While on pyrolysis of pure PS at 450C a dark-yellow even
brown liquid occurs in amount of approximately 90 %, the decomposition to gaseous
products runs only within 10 %. The dominant component in the pyroliquid is styrene. At
470C styrene occurs as 86 % wt. of the yield [17]. The thermal cracking of pure PET
starts already at 390C and it is accompanied by a considerable production of coke. As
a follow up of intensive coking, the reactor gets plugged (especially the cooling system)
by passing-over pyrolysis products, even in the case of various forms (shapes) of the
used PET in the batch reactor. The material balance of the products was poor, only at 70
%wt., out of which gases represented 20 %wt., residue materials were at 28.7 %wt. and
coke was at 20 %wt. [17]. When PET is pyrolysed, usually a large amount of residue is
formed, even at 700C (30 %wt.) [22].
Changes in composition of gaseous pyrolysis products were observed during heating
HDPE/LDPE/LLDPE/PP/PS/PVC/PET/mixture to final temperatures. After the pyrolysis
processes were finalised, the representative composition of liquid products was found out
gas-chromatographically. The overall material balances of the pyrolysis processes at end
temperatures 450C and 500C (Tab. 3) were calculated as subtraction of the mass of
solid residue and of the mass of liquid product from the mass of the raw material, by
which procedure the theoretical mass of yielded gases was found out. In the case of the
end-temperature 450C, the samples of the yielded gases were taken at temperatures
350C, 400C, 450C and one hour isothermically after reaching the temperature 450C.
In the case of the end-temperature 500C, the samples were taken at 400C, 450C, 500C
and one hour isothermically after reaching the temperature 500C.
The chromatographic analysis of gases has shown that gaseous pyrolysis products
from a seven-component mixture of plastic materials consist most of all from oxides of
carbon (Tab. 5 and Tab. 6.) Production of carbon dioxide sharply plunged with
temperature rising to 450C: from 6.4 % wt. to 0.1 % wt. At 500C the trend was from
4.2 mass% to 0.1 % wt. However, in a similar but reverse dependence, production of
carbon monoxide gets quickly prevalent. The averaged measured data have shown that
pyrolysis of a seven-component mixture of plastics produces about ten-times more
carbon monoxide compared to carbon dioxide. Carbon oxides (CO and CO2) are yielded in
such a large amount owing to thermal decarboxylation of PET. Gases and volatile solid
products appear in similar amounts. On the contrary, liquid products are barely observed
during thermal cracking of pure PET at 700C [22]. The gas consists mainly of carbon

M. Bajus, E. Hjekov/Petroleum & Coal 52(3) 164-172, 2010

168

oxides (32 %wt.), while the solid products show a broad spectrum of different
components with poor economic value. Especially organic acids, as benzoic acid (4.2 %
wt.), terephthalic acid was not quantified, can cause corrosion and blocking problems in
recycling facilities [22].
Table 4 Product distribution (%wt.) of components in gases obtained by thermal cracking
of polymer blend at 450C
Temperature, oC
Time of experiment,
min.
Components, %wt.
Carbon dioxide
Carbon monoxide
Methane
Ethane
Ethylene
Propane
Propene
Methylpropane
Butane
trans-2-Butene
1-Butene
Methylpropene
1,3- Butadiene
1,3-Pentadiene
cis-2-Butene
C4-hydrocarbons
Pentane
2 -Methyl-2-butene
1- Pentene
C5 - hydrocarbons
Benzene

350

400

450

450

17

24

32

92

6.4
1.6
9.2
11.8
11.4
29.9
traces
4.8
1.6
10.1
3.6
2.2
0.3
1.2
0.8
3.1
1.0
traces
0.4
0.7

Composition,
1.0
1.8
9.3
13.1
11.4
31.1
traces
5.1
1.7
10.8
3.7
2.4
0.3
1.2
1.1
3.7
1.1
traces
0.5
0.7

%wt.
0.8
59.0
3.1
4.3
12.1
2.4
6.7
traces
0.7
0.2
1.8
0.7
0.3
traces
0.1
6.1
1.6
0.1
traces
traces
0.1

0.1
31.2
6.7
12.8
14.0
8.9
16.1
0.1
2.1
0.3
2.8
1.2
0.4
traces
0.2
1.6
1.2
traces
0.2
0.1
traces

Average
composition
of gas
%wt.
2.1
22.6
3.3
8.9
12.7
8.5
21.0
traces
3.2
0.9
6.4
2.3
1.3
0.1
0.7
2.4
2.4
0.6
0.1
0.2
0.4

Table 5 Product distribution (%wt.) of components in gases obtained by thermal

cracking of polymer blend at 500oC
Temperature, oC
Time of experiment,
min.
Carbon dioxide
Carbon monoxide
Methane
Ethane
Ethylene
Propane
Propene
Methylpropene
Butane
trans-2- Butene
1- Butene
Methylpropene
cis - 2 - Butene
C4 - hydrocarbons
1,3 - Butadiene
1,3- Pentadiene
Pentane
2-Methyl-2-butene
1 - Pentene
C5- hydrocarbons
Benzene

400

450

500

500

26

36

46

116

Components, % wt.
2.3
4.2
0.4
traces
32.0
55.9
4.3
3.1
3.4
5.9
8.8
5.4
10.5
12.5
14.9
8.8
4.1
2.5
25.3
13.9
7.2
traces
traces
0.1
0.6
5.1
2.2
0.1
2.9
1.4
1.5
11.4
5.5
4.5
3.0
0.7
0.1
2.2
1.1
0.4
0.4
0.4
1.9
1.0
0.1
0.8
0.4
traces
1.3
5.0
4.5
2.4
1.3
0.1
traces
traces
traces
1.8
1.7
4.0
0.1
3.0
2.0

0.1
12.0
7.8
16.9
14.2
13.0
21.9
0.2
3.3
0.5
4.0
2.0
0.4
0.8
0.6
traces
1.8
traces
0.3
0.2
traces

Average
composition
of gas
1.8
25.0
4.6
9.2
13.0
7.1
17.1
0.1
2.8
1.2
5.6
2.5
0.9
0.5
0.9
0.3
3.1
0.9
0.1
1.9
1.7

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169

As to forming hydrocarbon gases that are produced during heating to 450C and 500C,
it can be stated that with increasing temperature production of methane is favoured at both
temperatures. Rising temperature has a positive effect also on production of ethane (from
9.2 %wt. to 12.8 %wt.) and ethylene (from 11.8 %wt. to 14 %wt.). Nevertheless, the
production of higher carbohydrates C3+ gets lower, at 450C: propane from 11.4 %wt. to
8.9 %wt.; propene from 29.9 %wt. to 16.1 %wt.; butane from 4.8 %wt. to 2.1 %wt.;
trans-2-butene from 1.6 %wt. to 0.3 %wt.; 1-butene from 10.1 %wt. to 2.8 %wt.;
methylpropene from 2.2 %wt. to 0.4 %wt.; pentane from 3.1 %wt. to 1.1 %wt. and
benzene from 0.7 %wt. to trace amounts (Tab. 5). Even at higher temperature, within
the temperature interval from 400C to 500C, the amount of methane in the reaction
products increases, from 3.1 %wt. to 7.8 %wt.. The amount of ethylene grows as well, from
10.5 %wt. to 14.1 %wt.. In a similar but reverse dependence, the production of ethane
falls from 8.8 %wt. to 5.9 %wt.; propane from 8.8 %wt. to 2.5 %wt.; propene from 25.3
%wt. to 7.2 %wt.; butane from 5.1 %wt. to 0.6 %wt.; trans-2-butene from 1.9 mass%
to 0.1 mass%; pentane from 5.0 mass% to 1.3 mass% and benzene from 3.0 %wt. to
0.1 %wt.. At isothermal conditions, at 500 C and reaction period 116 min, the
production of higher gaseous hydrocarbons from C3+ is on increase (Tab. 6).
On thermal cracking of mixed plastics at 450 C and 500C, no production of hydrogen
occurred. It is no surprise, because in comparable reaction conditions hydrogen was not
yielded in thermal cracking of individual (LDPE; LLDPE; PP) or mixed plastics (LDPE/PP;
HDPE/LDPE; HDPE/LDPE/LLDPE/PP; LLDPE/LDPE/PP/HDPE/PVC/PET/PS) [10, 15]. A pleasant
surprise is a prevailing representation of propene alongside ethylene. Formation of propene
and ethylene is welcome. These gaseous monomers belong to basic petrochemicals, even
in pyrolysis of hydrocarbons coming from crude oil fractions (naphtha) and from natural
gas (ethane, propane). Gaseous product obtained from pyrolysis runs at these different
temperatures mostly comprised C1 C4 hydrocarbon compounds that have high caloric
value. Consequently, the gaseous products could be utilized to supply the energy involved
in the pyrolysis process. The calculated caloric value valid for gaseous products formed at
these different temperatures was between 50.8 and 52.7 MJ/kg, which is comparable to
that pure methane gas with caloric value of 55.7 MJ/kg [18].
After each of the experiments had been finished, the pyroliquid of dark-green colour
and smell after pyrolytic gasoline was taken away from the drip. At 450C oil-waxes were
obtained in 65.9 % yield and at 500C in 62.4 % yield, compared to the feedstock (Tab. 3).
The oil-waxes represent a mixture of valuable hydrocarbons that can be utilised to synthesize
secondary chemicals in petrochemistry. The oil-waxes are of alkenic-aromatic character.
At first place they are 1-alkenes (- olefins) that are formed by thermal decomposition of
polyethylene and polypropylene, in agreement with the radical mechanism. The aromates
C6 C8 are mostly represented by styrene, as a result of thermal decomposition of polystyrene,
PET and PVC (Tab. 7 ).
Because PVC is present in the feedstock, gaseous and liquid chlorinated compounds,
of both organic and inorganic character, evolve during thermal cracking. To eliminate
them, washing by solution of sodium hydroxide was applied into the procedure. A caustic
soda wash traps mostly gaseous HCl that evolves by dehydrochlorination. In this work
chlorinated products from the reactions were not studied in detail as PVC in the feedstock
was present in quite a small amount (approximately 1 % mass). Meszaros [20] reported
that the pyrolysis of MWP in an Auger kiln reactor contained 3% mass of PVC (Conrad
Recycling Process). Lime was used in order to trap the HCl evolved, which resulted in
liquid products with 25 ppm of chlorine. The chlorinated hydrocarbons found in PE/PP/PS/PVC
degraded liquid products were also observed in PE/PP/PS/PVC/PET and MWP degraded
liquid products. The presence of PET in MWP produced the additional chlorinated hydrocarbons
that are similar to chlorinated hydrocarbons observed during the PE/PP/PS/PVC/PET
degradation liquid products. In addition, the presence of PET facilitated the formation of
higher organic chlorine content in liquid products and drastic decrease in the formation of
inorganic chlorine content [5, 19, 21].
Formation of aromatic hydrocarbons is characteristic for pyrolysis of mixed plastics
comprising PS, PET and PVC (Tab. 7). At 450C the aromates C6 C8 are represented by
17.4 %wt. and at 500C they are represented by 16.7 %wt.. Benzene, toluene, xylene,
ethylbenzene and styrene are represented in the yield by about 17 %wt., owing to the
thermal decomposition of polystyrene, polyethylene terephthalate and polyvinylchloride.

M. Bajus, E. Hjekov/Petroleum & Coal 52(3) 164-172, 2010

170

Table 7 The yields of gaseous and liquids components from thermal cracking of polymer
blend at 450oC and 500oC
Temperature, oC
Time of experiment, min.
Conversion to gases and liquids, %
Component
Carbon dioxide
Carbon monoxide
Methane
Ethane
Ethylene
Propane
Propene
Methylpropane
Butane
trans-2- Butene
1-Butene
Methylpropene
1,3-Butadiene
1,3-Pentadiene
cis-2-Butene
C4-hydrocarbons (unknown)
Pentane
1-Pentene
C5-hydrocarbons (unknown)
2-Methyl-2-butene
Benzene
1-Hexene
1-Heptene
Heptane
Toluene
1-Octene
1-Octane
Ethylbenzene
p- + m-Xylene
Styrene
o-Xylene
Nonane
1-Decene
Decane
1-Undecene
Undecane
1-Dodecene
Dodecane
1-Tridecene
Tridecane
1-Tetradecene
Tetradecane
1-Pentadecene
Pentadecane
1-Hexadecene
Hexadecane
1-Heptadecene
Heptadecane
Unknown

450
92
0.964
0.6
6.8
1.0
2.7
3.9
2.6
6.4
traces
1.0
0.3
1.9
0.7
0.4
0,1
0.2
0.7
3.2
1.0
0.1
0.2
2.6
2.7
1.8
1.9
2.8
1.4
1.6
1.8
1.0
7.5
1.7
1.4
1.6
1.0
1.6
1.4
1.3
1.1
1.2
1.1
1.2
0.8
0.8
0.8
0.5
0.6
0.5
0.5
18.6

500
116
0.979
Yields, % wt.
0.6
7.1
1.6
3.3
4.6
2.5
6.1
traces
1.0
0.4
2.0
0.9
0.3
0,1
0.3
1.7
2.0
0.8
0.7
0.3
4.0
3.1
1.9
1.2
2.0
1.6
1.1
2.0
0.9
6.1
1.6
0.9
1.9
0.9
1.7
0.9
1.3
1.1
1.2
1.0
1.1
0.8
0.8
0.7
0.6
0.5
0.5
0.4
19.5

The pure PS starts degrading around 300-400oC giving mainly styrene monomer,
benzene, toluene, some dimers and trimers as volatile products [23-27] and a cross-linked

M. Bajus, E. Hjekov/Petroleum & Coal 52(3) 164-172, 2010

171

residue above 400oC. It has been reported [23-28] that small amounts of C1-C4 hydrocarbons
are also produced during the pyrolysis of PS. The yields of the main degradation products
from pure PS increases with temperature except that of styrene-trimer. There is a considerable
decrease in the yields of all the degradation products with the 2,5 %wt. loading of PVC in
the PS matrix [23]. The stabilization effect has been explained on the basis of mechanism
involving interaction between the degrading products from the polymer components, thus
leading to a stable polymer network. The extend of interaction and hence the
stabilization.
The thermal cracking of the PET with following the decarboxylation and the reduction
of oxygen-containing compounds led to an increasing yield of aromatic hydrocarbons.
Especially benzene, toluene, styrene, naphthalene and biphenyls were obtained in high
yields from pure PET during thermal cracking at 700oC [22]. Ca(OH)2 can be used for the
decarboxylation of polyester as PET under pyrolysis conditions.
Thermal decomposition of a polymerous material (such as PE, PP), according to our
process, does not occur in the presence of polystyrene (PS), polyvinyl chloride (PVC), or
polyethylene terephthalate (PET). The point is that PS, PVC and PET decrease fuel production
and deteriorate the quality thereof. In the presence of PS, the production of aromatic
compounds that are not environmentally acceptable is increased. PVC and PET are also
among restrictive raw materials because in their presence an increased formation of coke
occurs on account of liquid products. The same results have recently been obtained by
other authors. PS degraded at around 350oC, mainly into viscous dark-coloured oil. The
formation of char only increased marginally up to 425oC, but dramatically increased at
450oC and 500oC, reaching up to 30 wt %. The oil products from PS even at 350oC, consisted
almost entirely of aromatic compounds, especially toluene, ethyl benzene and styrene.
Under increasing temperatures and residence times, the oil product from PS was preferentially
converted into char [14].
The mass rate of PE and PP volatilization was decreased in the presence of PVC, especially
at lower degradation temperatures (360oC to 450oC) and with increasing amounts of PVC.
This could be explained by the involvement of PE degradation fragments in reactions of polyene
structures resulting from DHC of PVC thus increasing the amount of high molecular weight
compounds that could not leave the reactor and thus remained in the reactor content.
Indeed, a considerable amount of reactor content corresponding to 10 wt % of the input
needed to be withdrawn every 30 minutes in order to avoid excessive accumulation of
material inside the reactor. In contrast, negligible accumulation was observed during
continuous flow degradation of PE and PP in the absence of PVC [29].
Our process uses only one batch reactor system. References to the advantageous use
of the batch reactor as compared to the continuous flow reactor are also made by other
authors [13]. The key difference is that the batch reaction system showed a relatively high
fraction of gasoline and a low fraction of heavy oil, whereas conversely the continuous
reaction system had a low fraction of gasoline and high fraction of heavy oil. The batch
reaction showed slightly faster production in the cumulative yield distribution of the liquid
product under the same degradation temperature programming in relation to that of the
continuous reaction system.
However, the maximum production rate of liquid products was obtained at a similar
elapsed time point, i.e. about 80 minutes: this was more strongly influenced by the
degradation temperature programming than by the reaction system itself. At the high
degradation temperature of 450oC, the heavy hydrocarbons were cracked into light
hydrocarbons, that is to say, gasoline-range products, and they were significantly more
cracked due to the longer elapsed time of the reactants in the reactor.
The batch reaction system showed a relatively high fraction of liquid components with
a low carbon number in the gasoline range, and a low fraction of heavy oil in relation to
the yields of the continuous reaction system.
3. Conclusion
This study presents results from investigation of the possibility for thermal cracking of
the model seven components mixed plastics into oils/waxes. The products of plastic cracking
were classified into three groups: gas, liquid (oil/wax) and solid residue. The presence of
PS, PVC and PET in the feedstock has predominant effect on the formation and yields of
gases and oil/waxes in the comparison with the thermal cracking of individual and mixed
polymers. It is found that the presence of PS, PVC and PET in model mixed plastics increased

M. Bajus, E. Hjekov/Petroleum & Coal 52(3) 164-172, 2010

172

the formulation of carbon monoxide and carbon dioxide in the gas and benzene, toluene,
xylenes, styrene in the liquid (oil/waxes) products.
Acknowledgement
We would like to thank the VEGA Scientific Grant Agency of the Slovak Republic and
the Commission for Chemistry and Chemical Technology, for financial support of this investigation
through the Research Project No. 1/0012/09.
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